Bicyclic 1,3-aminoalcohols, d8-metal complexes and hydrogenation processes

ABSTRACT

Bicyclic amino alcohols, whose amino group and hydroxy group are bonded in positions 1,3 adjacent to the bridge, for example  
                 
 
     are valuable ligands for metal complexes of the d-8 metals of the periodic table of elements. The metal complexes in question are catalysts or catalyst precursors for the asymmetric hydrogenation or asymmetric transfer hydrogenation with hydrogen donors of prochiral organic compounds with carbon double bonds or carbon/hetero atom double bonds, for example ketones and imines.

[0001] The present invention relates to bicyclic aminoalcohols; metalcomplexes with d8-metals and bicyclic aminoalcohols as ligands; aprocess for the asymmetric transfer hydrogenation of prochiral carbondouble bonds or hetero atom carbon bonds with alkanols as a source ofhydrogen; the use of bicyclic aminoalcohols as ligands in d8-metalcomplexes; and the use of metal complexes with d8-metals and bicyclicaminoalcohols as ligands for the asymmetric transfer hydrogenation ofprochiral carbon/carbon double bonds and hetero atom/carbon doublebonds.

[0002] In CA-A-2.239.970, a process is described for the asymmetrichydrogenation of carbon-hetero atom double bonds in for exampleprochiral ketones or imines using inorganic or organic hydrogen donors,for example secondary alkanols, in which process transition metalcomplexes are used as enantioselective catalysts, which contain chiralnitrogen-containing compounds as ligands. In the entire description,only ligands having a 1,2-aminoethanol basic structure are mentioned. WO98/42643 describes the same process, using the same or similar ligands,in which Ru, Rh and iridium complexes with cyclopentadienyl ligands areused as catalysts. In addition, open-chained 1,3-aminopropanols arementioned as ligands, but only moderate optical yields can be attainedwith these.

[0003] In J. Org. Chem. (1998), 63, pages 2749 to 2751, D. A. Alonso etal also describe the said process, whereby2-aza-1-hydroxymethylnorbomane is used as the bicyclic asymmetricligand. This likewise has a 1,2-aminoethanol basic structure and theNH-group is additionally bonded in the norbornane ring. Using thisligand, high conversions and optical yields are obtained.

[0004] It has now surprisingly been found that, during the asymmetrictransfer hydrogenation with asymmetric ligands of a 1,3-aminopropanolbasic structure in metal complexes as catalysts, high conversions andoptical yields may be attained when the optionally substituted OH and NHgroups are bound in the vicinity of the bridge of an at least bicyclicring system, and together with the metal atom, form a six-membered ring.

[0005] A first object of the invention is compounds of formula I in theform of the racemates thereof, mixtures of diastereoisomers orpredominantly pure diastereoisomers,

[0006] wherein

[0007] W signifies a direct bond or C₁-C₄-alkylene, X is a direct bondor C₁-C₄-alkylene, Y is C₁-C₄-alkylene, —O—, —S—, —NR₃—, —NR₃—CHR₄—,—NR₃—CR₄R₅, —SiR₄R₅—, —CHR₄O— or —CR₄R₅O—,

[0008] R₁ signifies hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl, C₆-C₁₀-aryl, or C₇-C₁₂-aralkyl,

[0009] R₂ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₆-C₁₀-aryl, orC₇-C₁₂-aralkyl, C₁-C₈-acyl, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkylaminocarbonyl, di(C₁-C₆-alkyl)aminocarbonyl, (R6)₂P(O)—, orR₆SO₂—,

[0010] R₃ signifies C₁-C₆-alkyl, cyclohexyl, phenyl or benzyl,

[0011] R₄ and R₅, independently of one another, are C₁-C₆-alkyl,cyclohexyl, phenyl or benzyl, and

[0012] R₆ is C₁-C₆-alkyl, C₁-C₆-halogenalkyl; or cyclohexyl, phenyl orbenzyl either unsubstituted or substituted by C₁-C₄-alkyl,C₁-C₄-halogenalkyl, or C₁-C₄-alkoxy; whereby aliphatic, saturated orethylenically unsaturated and/or aromatic hydrocarbon rings areoptionally condensed onto the rings of the bicyclic ring system; and theoptionally condensed bicyclic ring system is unsubstituted or issubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, cyclohexyl, C₆-C₁₀-aryl,C₇-C₁₂-aralkyl, C₁-C₄-alkyl-C₆-C₁₀-aryl, C₁-C₄-alkoxy-C₆-C₁₀-aryl,C₁-C₄-alkyl-C₇-C₁₂-aralkyl, C₁-C₄-alkoxy-C₇-C,₂-aralky; as well as theacid addition salts thereof.

[0013] In formula I, W preferably signifies C₁-C₃-alkylene, and mostpreferably C₁- or C₂-alkylene. In formula I, X preferably signifies adirect bond or C₁-C₃-alkylene, most preferably C₁- or C₂-alkylene. Informula I, Y preferably signifies C₁- or C₂-alkylene. In an especiallypreferred embodiment, W, X and Y are selected so that in the bicyclicring system of formula I they each form a 4- to 8-membered, preferably5- to 7-membered, most preferably 5- or 6-membered hydrocarbon ring.

[0014] R₁ as alkyl preferably contains 1 to 4 C-atoms. Examples of alkylare methyl, ethyl, n- and isopropyl, n—, iso- and tert.-butyl, as wellas the isomers of pentyl and hexyl.

[0015] R₁ as alkenyl preferably contains 2 to 4 C-atoms. Examples ofalkenyl are vinyl, allyl and crotonyl.

[0016] R₁ as cycloalkyl preferably contains 4 to 7 C-atoms. Examples ofcycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred.

[0017] R₁ as cycloalkenyl preferably contains 4 to 7 C-atoms. Examplesof cycloalkyl are cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclohexenyl, cycloheptenyl and cyclooctenyl. Cyclopentenyl andcyclohexenyl are preferred.

[0018] R₁ as aryl may be for example phenyl or naphthyl.

[0019] R₁ as aralkyl may be for example phenyl-C₁-C₄-alkyl ornaphthyl-C₁-C₄-alkyl. Benzyl and phenylethyl are preferred.

[0020] In a preferred embodiment, R₁ is hydrogen, C₁-C₄-alkyl, allyl,cyclopentyl, cyclohexyl, phenyl or benzyl. R₁ is most preferablyhydrogen.

[0021] R₂ as alkyl preferably contains 1 to 4 C-atoms. Examples of alkylare methyl, ethyl, n- and isopropyl, n-, iso- and tert.-butyl, as wellas the isomers of pentyl and hexyl.

[0022] R₂ as cycloalkyl preferably contains 4 to 7 C-atoms. Examples ofcycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred.

[0023] R₂ as aryl may be for example phenyl or naphthyl.

[0024] R₂ as aralkyl may be for example phenyl-C₁-C₄-alkyl ornaphthyl-C₁-C₄-alkyl Benzyl and phenylethyl are preferred.

[0025] R₂ as alkoxycarbonyl is preferably C₁-C₄-alkoxycarbonyl. Examplesof alkoxy are methoxy, ethoxy, n- and isopropyloxy, n-, iso- andtert.-butyloxy, as well as the isomers of pentyloxy and hexyloxy. R₂ ispreferably tert.-butyloxycarbonyl.

[0026] When R₂ is the radical (Rr)₂P(O)— or R₆-SO₂—, R₆ is preferablyC₁-C₄-alkyl, C₁-C₄-halogen-alkyl, or phenyl or benzyl eitherunsubstituted or substituted by methyl, ethyl, trifluoromethyl, methoxyor ethoxy. Halogen in the halogen moiety is preferably chlorine, andmore preferably fluorine. Examples of the radical R₆-SO₂- are methyl-,ethyl-, n- and iso-propyl—, n- and iso-butyl-, phenyl-, benzyl-,methylphenyl-, ethylphenyl-, dimethylphenyl-, methylbenzyl-,dimethylbenzyl-, trifluoromethylphenyl- andbis(trifluormethyl)phenylsulfonyl. Examples of the radical (R₆)₂P(O)—are dimethyl—, diethyl—, diphenyl- and di-p-toluyloxyphosphinyl.

[0027] If R₂ signifies acyl, it preferably contains 1 to 6, mostpreferably 1 to 4 C-atoms. A few examples are formyl, acetyl, propionyl,butyroyl and benzoyl.

[0028] If R₂ signifies alkylaminocarbonyl or di(alkyl)aminocarbonyl, thealkyl group preferably contains 1 to 4, most preferably 1 or 2 C-atoms.A few examples are methylamino-, dimethylamino-, ethylamino-,diethylamino-, methyl-ethylamino-, n- or iso-propylamino- and di-n- or-iso-propylaminocarbonyl

[0029] If R₃ is alkyl, it preferably contains 1 to 4 C-atoms. R₃ ispreferably ethyl and most preferably methyl.

[0030] If R₄ and R₅ are alkyl, it preferably contains 1 to 4 C-atoms. R₄and R₅ are preferably methyl.

[0031] In a preferred embodiment, R₂ is C₁-C₄-alkyl, cyclopentyl,cyclohexyl, phenyl, benzyl, C₁-C₄-alkoxycarbonyl or the radical R₆—SO₂—,wherein R₆ is C₁-C₄-alkyl, C₁-C₄-fluoroalkyl, or phenyl eitherunsubstituted or substituted by one or two methyl or trifluoromethyl.

[0032] If hydrocarbon rings are condensed onto the bicyclic ring system,then these are preferably C₆-C₁₀-aryl (for example benzene ornaphthaline), C₃-C₈-cycloalkyl, preferably C₅-C₇-cycloalkyl, orC₄-C₈-cycloalkenyl, preferably C₅-C₇-cycloalkenyl.

[0033] Preferred substituents for the optionally condensed bicyclic ringsystem are C₁-C₄-alkyl (for example methyl, ethyl, n- and iso-propyl andthe isomers of butyl, and C₁-C₄-Alkoxy (for example methoxy, ethoxy, n-and iso-propyloxy and butyloxy), phenyl, benzyl, C₁-C₂-alkylphenyl.

[0034] Of the compounds according to the invention, those that areespecially preferred are those of formula Ia,

[0035] wherein Y signifies —CH₂— or —CH₂CH₂—, and R₂ is H, C₁-C₄-alkyl(especially methyl or ethyl), or the radical of formula R₆—SO₂—, and R₆is C₁-C₄-alkyl (especially methyl or ethyl), phenyl or phenyl (forexample p-toluyl), which is substituted by C₁-C₄-alkyl (especiallymethyl or ethyl) or by trifluoromethyl.

[0036] Acids for the formation of acid addition salts may be selectedfrom inorganic and organic acids. Examples of organic acids arecarboxylic acids, phosphonic acids and sulfonic acids, such as formicacid, acetic acid, fluoroacetic acids, chloroacetic acids, propionicacid, oxalic acid, malonic acid, benzoic acid, methylphosphonic acid,phenylphosphonic acid, p-toluyl-phosphonic acid, methylsulfonic acid,trifluoromethylsulfonic acid, phenylsulfonic acid and p-toluylsulfonicacid. Examples of organic acids are hydrohalic acids, especially HCl,HBr and HI, sulphuric acid, phosphorous acid, phosphoric acid,tetrafluoroboric acid and hexafluorophosphoric acid.

[0037] The compounds according to the invention may be produced fromknown unsaturated bicyclic carboxylic acids or those produced accordingto known or analogous methods.

[0038] A further object of the invention is a process for thepreparation of compounds of formula I, which is characterised in that

[0039] (a) a compound of formula II

[0040] wherein W, X and Y are defined as indicated above, is reactedwith a phosphoric acid ester azide in the presence of an alcohol R—OH,wherein R signifies C₁-C₆-alkyl, C₅-C₈-cycloalkyl,C₅-C₈-cycloalkyl-C₁-C₄-alkyl, benzyl, or benzyl substituted byC₁-C₄-alkyl, to form a compound of formula III,

[0041] b) the compound of formula III is cyclised with bromine, iodineor an electrophilic brominating or iodising agent to form a compound offormula IV, wherein X′ is Br or I,

[0042] c) in the compound of formula IV, the halogen is substituted byhydrogen to form a compound of formula V,

[0043] d) the compound of formula V is hydrolysed or reduced to thecompound of formula VI,

[0044] e) or in the compound of formula V, the hydrogen atom of the NHgroup is substituted by the group R′₂ to form compounds of formula VII,wherein R′₂ signifies C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₆-C₁₀-aryl, orC₇-C₁₂-aralkyl, and then the compounds of formula VII are hydrolysed orreduced to compounds of formula VIII,

[0045] f) or the compounds of formula VI are reacted withC₁-C₆-alkoxycarbonates, C₁-C₆-alkylamino- or C₁-C₆-dialkylamino-carbonylhalides, C₁-C₈-carboxylic acid halides, C₁-C₆-alkoxycarbonyl halides,(R₆)₂P(O)-halides or R₆-SO₂-esters or halides, to form compounds offormula IX, wherein R″₂ signifies C₁-C₆-alkoxycarbonyl, C₁-C₈-acyl,C₁-C₆-alkylamino—, C₁-C₆-dialkylaminocarbonyl or the groups (R₆)₂P(O)-und R₆-SO₂-.

[0046] g) and in compounds of formulae VI, VII and IX, the OH group isetherified to compounds of formula X, R′, signifies C₁-C₆-alkyl,C₂-C₆-alkenyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl, C₆-C₁₀-aryl, orC₇-C₁₂-aralkyl, and R₂ is defined as indicated for formula I,

[0047] Another object of the invention is compounds of formula V, whichare valuable intermediates in the preparation of the compounds accordingto the invention,

[0048] wherein W, X and Y are defined as indicated for formula I,whereby aliphatic, saturated or ethylenically unsaturated and/oraromatic hydrocarbon rings are optionally condensed onto the rings ofthe bicyclic ring system; and the optionally condensed bicyclic ringsystem is unsubstituted or is substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy,cyclohexyl, C₆-C₁₀-aryl, C₇-C₁₂-aralkyl, C₁-C₄-alkyl-C₆-C₁₀-aryl,C₁-C₄-alkoxy-C₆-C₁ ₀-aryl, C₁-C₄-alkyl-C₇-C₁₂-aralkyl orC₁-C₄-alkoxy-C₇-C₁₂-aralkyl.

[0049] The reaction (Curtius reaction) of process step a) is known perse and is described by K. Ninomiya et al. in Tetrahedron Vol. 30, pages2151-2157 (1974). Details are given in the examples.

[0050] The reaction of process step b) is likewise known and isdescribed by S. Takano et al. in Heterocyles Vol. 19, No. 7, pages1243-1245 (1982). Known electrophilic halogenation agents are forexample N-Br- or N-1-carboxylic acid and -sulfonic acid imides (N—Br— orN—I— succinimide). Details are given in the examples.

[0051] The reaction of process step c) is generally known. Thesubstitution by hydrogen may be carried out with metal hydrides and ispreferably carried out catalytically with hydrogen in the presence ofnoble metal catalysts.

[0052] The hydrolysis of process steps d) and e) is a generally knownreaction which is familiar to a person skilled in the art and which usesaqueous acids or aqueous bases. Metal hydrides are preferably used forreduction, for example LiAlH₄.

[0053] The formation of secondary amines in process step e) bysubstitution of a hydrogen atom in the NH₂ group is a reaction that hasbeen known for a long time. Substitution reagents that are primarilyemployed are hydrocarbon chlorides, bromides and iodides.

[0054] The preparation of the compounds of formula IX in process step fby means of amino-carbonylation, alkoxycarbonylation, acylation,phosphorylation or sulfonation is similarly a reaction which has beenknown for a long time and which is described more fully in the examples.The etherification of process step g) by means of alkylation agents suchas alkyl halides or alkyl sulfates is also generally known and is notdescribed in detail here.

[0055] Compounds of formula I, in which R₂ is methyl, are alsoobtainable by reduction of carbamoyl compounds of formula IX, in whichR″₂ signifies C₁-C₆-alkoxycarbonyl. The reduction agents used aresuitably metal hydrides, such as LiAlH₄.

[0056] Addition salts are obtained in a simple manner, by reactingcompounds of formula I with acids in equimolar amounts.

[0057] Diastersoisomeric mixtures and pure diastereoisomers may beobtained by the usual separation processes, if they have not alreadybeen formed during synthesis. Conventional separation processes arecrystallisation and chromatography.

[0058] The reactions of process steps a) to g) may be carried outwithout or in the presence of an inert solvent, whereby one solvent ormixtures of solvents may be used. Suitable solvents are, for example,aliphatic, cycloaliphatic and aromatic hydrocarbons (pentane, hexane,petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene,xylene), aliphatic halogen-hydrocarbons (methylene chloride, chloroform,di- and tetrachloroethane), nitrites (acetonitrile, propionitrile,benzonitrile), ethers (diethylether, dibutylether,tert.-butylmethylether, ethylene glycol dimethylether, ethylene glycoldiethylether, diethylene glycol dimethylether, tetrahydrofuran, dioxane,diethylene glycol monomethyl- or monoethylether), ketones (acetone,methyl isobutyl ketone), carboxylates and lactones (ethyl and methylacetate, valerolactone), N-substituted lactams (N-methylpyrrolidone),carboxamides (dimethylamide, dimethylformamide), acyclic ureas (dimethylimidazoline), and sulfoxides and sulfones (dimethyl sulfoxide, dimethylsulfone, tetramethylene sulfoxide, tetramethylene sulfone) and alcohols(methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, diethylene glycol monomethyl ether) andwater. The solvents may be used on their own or in a mixture of at leasttwo solvents.

[0059] The reaction may be carried out whilst cooling, for example to−30° C., at room temperature or at elevated temperature, for example 30to 250° C. Normally, equimolar amounts of the reactants are used, or anexcess of one reactant. Isolation of the reaction products may beeffected for example by distillation, crystallisation and/or extraction;and the products may be purified by distillation, recrystallisationand/or chromatography.

[0060] The compounds of formula I according to the invention areexcellent ligands for metal complexes of the d8 metals of the periodictable of elements, which can be used as catalysts or precursors ofcatalysts, especially during hydrogenation and transfer hydrogenationusing hydrogen donors. If prochiral unsaturated compounds are used, ahigh excess of optical isomers can be induced in the synthesis oforganic compounds and a high chemical conversion can be achieved.

[0061] A further object of the invention is metal complexes of metalsselected from the secondary group VII of the periodic table of elementswith compounds of formula I as ligands. The selected metals within thecontext of the invention are also called d-8 metals.

[0062] Depending on the oxidation number and coordination number of themetal atom, the metal complexes may contain further ligands and/oranions. The metal complexes in question may also be cationic metalcomplexes. Analogous metal complexes of this type, and the preparationthereof (in situ or as isolated compounds), have been described inliterature many times (see for example A. Fujii et al., JACS, 118,(1996), 2521ff. and J. Takehara et al., Chem. Communication (Cambridge),as well as CA-A-2,239,970 and WO 98/42643).

[0063] The ligands according to the invention may exist in the metalcomplexes as neutral ligands or as ionic amide ligands. In addition, themetal complexes may contain identical or different, monodentate orbidentate, anionic or non-ionic ligands. They may also be complex saltswith anions of an oxyacid or complex acid. Anions and anionic ligandsserve to balance the charge of the oxidation stages of the metal.

[0064] The d8 metal may be selected from the group Fe, Ni, Co, Rh, Pd,Ir, Ru and Pt, and preferably from the group Rh, Ir and Ru, the metalhaving the oxidation degrees 0, 1, 2, 3 or 4.

[0065] The above-described preferences and embodiments apply to thecompounds of formula I.

[0066] Monodentate non-ionic ligands may be selected for example fromthe group of olefins (for example ethylene, propylene), solvatisingsolvents (nitriles, linear or cyclic ethers, optionally N-alkylatedamides and lactams, amines, phosphines, alcohols, carboxylic acidesters, sulfonic acid esters), nitrogen monoxide and carbon monoxide.

[0067] Further non-ionic (neutral) ligands are arenes with for example 6to 18 carbon atoms. The arenes in question may be monocycles orcondensed ring systems. The arenes preferably contain 6 to 14, mostpreferably 6 to 10 carbon atoms. The arenes may be unsubstituted orsubstituted, for example by C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-fluoroalkyl, C₁-C₄-hydroxyalkyl, hydroxyl, halogen, cyano, —CO₂H,—SO₃H, carboxy-C₁-C₄-alkyl or carbamide.

[0068] Arenes preferably contain 6 to 18, more preferably 6 to 14, mostpreferably 6 to 10 carbon atoms. They may be unsubstituted orsubstituted by C₁-C₆-alkyl, C₁-C₈-alkoxy or halogen. A few examples ofarenes and heteroarenes are benzene, naphthalene, anthracene, indan,fluorene, biphenyl, indan, toluene, hexamethylbenzene, 1,3,5-mesityleneand cumene.

[0069] Monodentate anionic ligands may be selected for example from thegroup hydride, halide (F, Cl, Br, I), pseudohalide (cyanide, cyanate,isocyanate) and anions of carboxylic acids, sulfonic acids, phosphonicacids (carbonate, formate, acetate, propionate, methylsulfonate,trifluoromethylsulfonate, phenylsulfonate, tosylate), allyls (allyl,2-methallyl), and optionally substituted cyclopentadienylene(cyclopentadienyl, methylcylopentadienyl, dimethyl-cyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,penta-methyl-cyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl).

[0070] Bidentate non-ionic ligands may be selected for example from thegroup of linear or cyclic diolefins (for example hexadiene,cyclohexadiene, cyclooctadiene, norbornadiene), dinitriles(malonodinitrile), optionally N-alkylated dicarboxylic acid diamides,diamines, diphosphines, diols, acetonyl acetonates, dicarboxylic aciddiesters, disulfonic acid diesters and amino-alcohols.

[0071] Bidentate anionic ligands may be selected for example from thegroup of anions of dicarboxylic acids, disulfonic acids, diphosphonicacids (for example oxalic acid, malonic acid, succinic acid, maleicacid, methylenedisulfonic acid and methylenediphosphonic acid) andbridged cyclopentadienylene [methylene-biscyclopentadienyl,methylene-bis-(tetramethylcyclopentadienyl),biscyclopentadienyl-dimethylsilane)].

[0072] Preferred metal complex salts are those with anions selected fromthe group Cl, Br, I, ClO₄, CF₃SO₃ ⁻, CH₃SO₃ ⁻, HSO₄ ⁻, BF₄ ⁻, B(phenyl)₄⁻, PF₆ ⁻, SbCl₆ ⁻, AsF₆ ⁻, SbFB or B(3,5-CF₃-C₆H₅)₄ ⁻.

[0073] A preferred group of metal complexes comprises those of formulaXI,

[Ru(arene)(L)(A)]   (XI),

[0074] wherein A is hydride or chloride, and L signifies a ligand offormula I. The above-mentioned embodiments and preferences apply toarene.

[0075] Another preferred group of metal complexes comprises those offormula XII,

[Me(diene)(L)(A₁)]  (XII),

[0076] wherein Me is Rh or Ir, diene signifies an open-chained or cyclicdiene, L represents a ligand of formula I, and A₁ signifies halide,preferably chloride, bromide or iodide. The above-mentioned embodimentsand preferences apply to diene and the ligands of formula I. Thecomplexes of formula XII are obtainable by reacting the ligand L with[Me(diene)A₁)]₂. A further preferred group of metal complexes comprisesthose of formula XIII,

[Me₁Cp(L)A₂]  (XIII),

[0077] wherein Me, signifies Rh, Ir or Ru, A₂ is hydride or halide,preferably chloride, L signifies a ligand of formula I, and Cprepresents an optionally substituted cyclopentadienyl or indenyl. Theabove-mentioned embodiments and preferences apply to the ligands offormula I and cyclopentadienyls as well as indenyls. The complexes offormula XIII are obtainable by reacting the ligand L with [Me₁CpA)]₂.

[0078] The metal complexes according to the invention are prepared bymethods known in literature (see also CA-A-2,239,970 and WO 98/42643).

[0079] The metal complexes according to the invention are homogeneouscatalysts or are catalyst precursors that can be activated under thereaction conditions, and they may be used for example for thehydrogenation of unsaturated organic compounds.

[0080] The metal complexes are preferably used for the asymmetrichydrogenation of prochiral compounds with carbon/carbon or carbon/heteroatom multiple bonds, in particular double bonds. The metal complexes areespecially suitable for transfer hydrogenation using hydrogen donors.Hydrogenation of this kind with soluble homogeneous metal complexes isdescribed for example in Pure and Appl. Chem., Vol. 68, No. 1, pp.131-138 (1996).

[0081] A further object of the invention is therefore the use of themetal complexes according to the invention as homogeneous catalysts forhydrogenation, preferably transfer hydrogenation with hydrogen donors,of prochiral compounds having carbon/carbon or carbon/hetero atommultiple bonds, especially carbon/hetero atom double bonds.

[0082] A further aspect of the invention is a process for the asymmetrichydrogenation with hydrogen, or transfer hydrogenation with hydrogendonors, of prochiral compounds with carbon- or carbon/hetero atommultiple bonds, especially carbon/hetero atom double bonds, which ischaracterised in that the compounds are reacted at low to elevatedtemperatures in the presence of catalytic quantities of a metal complexaccording to the invention.

[0083] Preferred prochiral, unsaturated compounds to be hydrogenated maycontain one or more, identical or different groups C═C, C═N and/or C═O,in open-chained or cyclic organic compounds, whereby the groups C═C, C═Nand/or C═O may be part of a ring system or may represent exocyclicgroups. The prochiral, unsaturated compounds in question may be alkenes,cycloalkenes, heterocycloalkenes, and also open-chained or cyclicketones, ketimines and ketohydrazones. They may correspond, for example,to formula XIV,

R₇R₈C═D (XIV),

[0084] wherein R₇ and R₈ are selected in such a way that the compound isprochiral, and, independently of one another, represent an open-chainedor cyclic hydrocarbon radical or hetero-hydrocarbon radical with heteroatoms selected from the group O, S and N, containing 1 to 30, preferably1 to 20 carbon atoms;

[0085] D is O or a radical of formula C═R₉R₁₀ or NR₁₁;

[0086] R₉ and R₁₀, independently of one another, have the samesignificance as R₇ and R₈;

[0087] R₁₁, signifies hydrogen, C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy,C₃-C₁₂-cycloalkyl, C₃-C₁₂-cycloalkyl-C₁-C₆-alkyl,C₃-C₁₁-heterocycloalkyl, C₃-C₁₂-heterocycloalkyl-C₁-C₆-alkyl,C₆-C₁₄-aryl, C₅-C₁₃-hetero-aryl, C₇-C₁₆-aralkyl or C₆-C₁₄-heteroaralkyl;

[0088] R₇ and R₈, together with the carbon atom to which they arebonded, form a hydrocarbon ring or hetero-hydrocarbon ring with 3 to 12ring members;

[0089] R₇ and R₉, together with the C═C-group to which they are bonded,each form a hydrocarbon ring or hetero-hydrocarbon ring with 3 to 12ring members;

[0090] R₇ and R₁₁, together with the C═N-group to which they are bonded,each form a hydrocarbon ring or hetero-hydrocarbon ring with 3 to 12ring members; the hetero atoms in the heterocyclic rings are selectedfrom the group O, S and N; and R₇, R₈, R₉, R₁₀ and R₁₁ are unsubstitutedor substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, cyclohexyl, C₆-C₁₀-aryl,C₇-C₁₂-aralkyl, C₁-C₄-alkyl-C₆-C₁₀-aryl, C₁-C₄-alkoxy-C₆-C₁₀-aryl,C₁-C₄-alkyl-C₇-C₁₂-aralkyl, C₁-C₄-alkoxy-C₇-C₁₂-aralkyl, —OH, —CO—OR₇,—CO—NR₈R₉ or —NR₈R₉, wherein R₇ is H, an alkali metal, C₁-C₆-alkyl,cyclohexyl, phenyl or benzyl, and R₈ and R₉, independently of oneanother, are hydrogen, C₁-C₆-alkyl, cyclohexyl, phenyl or benzyl, or R₈and R₉ together signify tetramethylene, pentamethylene or3-oxapentylene.

[0091] Examples and preferences of substituents have already beenmentioned.

[0092] R₇ and R₈ may be for example C₁-C₂₀-alkyl, and preferablyC₁-C₁₂-alkyl, C₁-C₂₀-heteroalkyl and preferably C₁-C₁₂-heteroalkyl withhetero atoms selected from the group O, S and N, C₃-C₁₂-alkyl andpreferably C₄-C₈-cycloalkyl, C-bonded C₃-C₁₁-heterocycloalkyl andpreferably C₄-C₈-heterocycloalkyl with hetero atoms selected from thegroup O, S and N, C₃-C₁₂-cycloalkyl-C₁-C₆-alkyl and preferablyC₄-C₈-cycloalkyl-C₁-C₆-alkyl, C₃-C₁₁-heterocycloalkyl-C₁-C₆-alkyl andpreferably C₄-C₈-heterocycloalkyl-C₁-C₆-alkyl with hetero atoms selectedfrom the group O, S and N, C₆-C₁₄-aryl and preferably C₆-C₁₀-aryl,C₅-C₁₃-heteroaryl and preferably C₅-C₉-heteroaryl with hetero atomsselected from the group O, S and N, C₇-C₁₅-aralkyl and preferablyC₇-C₁₁-aralkyl, C₆-C₁₂-hetero-aralkyl and preferablyC₆-C₁₀-hetero-aralkyl with hetero atoms selected from the group O, S andN.

[0093] When R₇ and R₈, R₇ and R₉, or R₇ and R₁₁ each together form ahydrocarbon ring or hetero-hydrocarbon ring, the ring preferablycontains 4 to 8 ring members. The hetero-hydrocarbon ring may containfor example 1 to 3, preferably one or two hetero atoms.

[0094] In formula XIV, D is preferably the radical NR₁₁, most preferablyO.

[0095] R₁₁ preferably signifies hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₄-C₈-cycloalkyl, C₄-C₈-cyclo-alkyl-C₁-C₄-alkyl,C₄-C₁₀-heterocycloalkyl, C₄-C₁₀-heterocycloalkyl-C₁-C₄-alkyl,C₆-Cl₀-aryl, C₅-C₉-heteroaryl, C₇C₁₂-aralkyl and C₅-C₁₃-heteroaralkyl.

[0096] A few examples of prochiral ketones are acetophenone,4-methoxyacetophenone, 4-tri-fluoromethylacetophenone,4-nitroacetophenone, 2-chloroacetophenone, corresponding acetophenonebenzylimines, unsubstituted or substituted benzocyclohexanone orbenzocyclopentanone, and imines from the group unsubstituted orsubstituted tetrahydroquinoline, tetrahydropyridine and dihydropyrrole.

[0097] Hydrogen donors are, for example, primary and secondary alcohols,primary and secondary amines, carboxylates, carboxylic acids and theirammonium salts, readily dehydrogenatable hydrocarbons and reductionagents. The hydrogen donors are used in at least equimolar amounts or inan excess, based on the compound to be hydrogenated. The excess may beup to 5 mols and more, especially if suitable hydrogen donors serve assolvents at the same time. Hydrogen donors may be used in a mixture withadditional hydrogen.

[0098] The primary and secondary alcohols preferably contain 1 to 10carbon atoms, more preferably 2 to 6 carbon atoms, and most preferably 3or 4 carbon atoms. A few examples are methanol, ethanol, n- andisopropanol, n- and isobutanol, 1-, 2- or 3-pentanol, 1-, 2- or3-hexanol, cyclopentanol, cyclohexanol, benzyl alcohol and menthol.Secondary alcohols are preferred, particularly isopropanol andisobutanol.

[0099] The primary and secondary amines may contain, for example, 1 to20 carbon atoms, preferably 2 to 16 carbon atoms, most preferably 3 to12 carbon atoms. A few examples are ethylamine, n- and isopropylamine,n- and isobutylamine, pentylamine, hexylamine, benzylamine, piperidine,morpholine, cyclohexylamine, diethylamine, di-n- or -isopropyl-amine,di-n- or -isobutylamine, dipentylamine and dihexylamine. Primary aminesare preferred, especially primary amines with a branched alkyl group,for example isopropylamine and isobutylamine.

[0100] The carboxylic acids are preferably aliphatic or cycloaliphaticcarboxylic acids, with for example 1 to 10 carbon atoms, preferably 1 to4 carbon atoms. They may be substituted by hydroxyl groups, especiallyin beta-position to the carboxyl group. A few examples are formic acid,lactic acid and ascorbic acid. Carboxylates may be derived from theabove-mentioned carboxylic acids, and contain for example a C₁-C₂₀-alkylgroup, preferably C₁-C₄-alkyl group in the ester group.

[0101] The ammonium salts may be derived from the above-mentionedcarboxylic acids and primary, secondary, tertiary or quaternaryammonium. The ammonium may contain for example 1 to 20, preferably 2 to16, most preferably 3 to 12 carbon atoms. Tri(C₁-C₄-alkyl)ammonium isespecially suitable. A few examples of ammonium are methylammonium,dimethylammonium, trimethylammonium, ethylammonium, diethylammonium,triethylammonium, methylethylammonium, isopropyl-diethylamine,di-isopropylethylamine. Trialkylammonium formate, especially triethylformate, are preferred in particular. The molar ratio of carboxylic acidto amine in the reaction mixture is in general approximately 5 to 2.

[0102] Readily dehydrogenatable hydrocarbons are for example those thathave a tendency to aromatise or to form conjugated systems. A fewexamples are cyclohexadiene, cyclohexene, tetraline, dihydrofuran andterpene.

[0103] Suitable reduction agents are for example hydrazine andhydroxylamine.

[0104] Low to elevated temperature in the context of the invention canmean for example −20 to 150° C., preferably −10 to 100° C., mostpreferably 10 to 80° C. The optimum yields are generally better at lowertemperature than at higher temperatures. In hydrogenation, the hydrogenpressure may be for example from 10⁵ to 2×10⁷ Pa (Pascal). Transferhydrogenation is preferably carried out at normal pressure or slightexcess pressure.

[0105] Catalysts are preferably used in amounts of 0.0001 to 10 mol %,more preferably 0.001 to 10 mol %, most preferably 0.01 to 5 mol %,based on the compound to be hydrogenated.

[0106] The reaction can be carried out without solvents or in thepresence of inert solvents. Solvents are generally known, and the choicethereof depends primarily on the solubility of the substrate and metalcomplexes. Suitable solvents have already been named.

[0107] The reaction may take place in the presence of bases. Suitablebases are, for example, alkali and alkaline earth bases [LiOH, NaOH,KOH, Mg(OH)₂ and Ca(OH)₂] alkali metal alcoholates of C₁-C₆-alkanols(lithium, sodium, potassium, cesium methylate, ethylate, -n- and-isopropylate, -n- , -iso- and -t-butylate), alkali metal carbonates(Li₂CO₃, Na₂CO₃, K₂CO₃, KHCO₃) and alkali metal carboxylates ofC₁-C₆-carboxylic acids (formates, acetates, propionates and butyrates).The molar ratio of catalyst metal to base is, for example, from 1:1 to1:4, preferably 1:1 to 1:2.

[0108] The metal complexes used as catalysts may be added as separatelyproduced, isolated compounds, or may also be formed in situ prior to thereaction and then mixed with the substrate to be hydrogenated.

[0109] Hydrogenation may be carried out continuously or intermittentlyin various types of reactor. Preference is given to those reactors whichallow propitious blending and good heat removal, e.g. loop reactors.This type of reactor has proved favourable especially when using smallamounts of catalyst.

[0110] The hydrogenated organic compounds which may be producedaccording to the invention are active substances or intermediates in thepreparation of such substances, especially in the preparation ofpharmaceuticals and agrochemicals. Thus for exampleo,o-dialkylarylketamine derivatives, especially those with alkyl and/oralkoxyalkyl groups, are effective as fungicides, especially asherbicides. The derivatives in question may be amine salts, acid amides,e.g. of chloroacetic acid, tertiary amines and ammonium salts (see e.g.EP-A-0 077 755 and EP-A-0 115 470).

[0111] The following examples illustrate the invention.

[0112] A) Preparation of ligands

EXAMPLE A1Preparation of 1-amino-3-hydroxy-norbornane (A1)

[0113] a) Preparation of

[0114] 18 g of (−)(1S,2S)-5-norbornene-2-carboxylic acid are dissolvedin 360 ml of toluene. After adding 19.1 ml of triethylamine and 31 ml ofphosphoric acid diphenylester azide, stirring is effected for 30 minutesat room temperature. Subsequently, 16.1 ml of benzyl alcohol are added.The reaction mixture is stirred under reflux for 17 hours and thencooled to room temperature. After adding 350 ml of toluene, the mixtureis washed twice with saturated aqueous NaCl solution, dried over MgSO₄and concentrated by evaporation on a rotary evaporator. From theresidue, the title compound (a) is obtained in the form of an oil byflash chromatography (SiO₂ 60F I ethyl acetate / hexane, 1:5) (16.2 g,51% of theory). ¹H-NMR (400 Hz, DMSO_(d6)) δ: 0.82 (1H); 1.30 (2H); 2.0(1H); 2.77 (1H); 3.0 (1H); 4.0 (1H); 5.0 (2H); 5.95 (1H); 6.25 (1H);6.82 (1H); 7.35 (5H).

[0115] b) Preparation of

[0116] 15.85 g of (a) are dissolved in 180 ml of dichloromethane, mixedwith 19.84 g of iodine and subsequently stirred for 1 hour at roomtemperature. The reaction mixture is diluted with 1 liter of ethylacetate, washed with aqueous sodium bisulfite solution (2×) and water(1×), dried over MgSO₄ and then concentrated by evaporation on a rotaryevaporator. The residue is mixed with 200 ml of tert.-butylmethyletherand stirred for 15 minutes at room temperature. The mixture is filtered,washed with tert.-butylmethylether (2×), to produce the title compound(b) as a yellow solid (15.9 g, 87% of theory). ¹H-NMR (400Hz, CDCl₃) δ:1.47 (1H); 1.70 (1H); 2.15 (2H); 2.45 (1H); 2.65 (1H); 3.85 (1H); 3.90(1H); 5.21 (1H); 6.52 (1H).

[0117] c) Preparation of

[0118] 15.5 g of (b) are dissolved in 450 ml of ethanol, and afteradding 14 ml of triethylamine and 0.9 g of PtO₂,H₂O, are hydrogenated atnormal pressure. After 2 hours, the reaction mixture is filtered andconcentrated by evaporation on a rotary evaporator. The residue isdissolved in 500 ml of dichloromethane, washed with saturated aqueoussodium bicarbonate solution (1×) and with saturated aqueous NaClsolution (1×), dried over MgSO₄ and then concentrated by evaporation ona rotary evaporator. From the residue, the title compound (c) isobtained as a light beige solid by flash chromatography (SiO₂ 60F /dichloromethane / methanol, 15:1) (6.2g, 73% of theory). ¹H-NMR (400Hz,CDCl₃) δ: 1.40 (2H); 1.50 (2H); 2.08 (1H); 2.15 (2H); 2.43 (1H); 3.81(1H); 4.82 (1H); 6.35 (1H).

[0119] d) Preparation of compound A1

[0120] 19 g of (c) are dissolved in 450 ml of ethanol, mixed with 250 mlof 4N aqueous sodium hydroxide solution and subsequently stirred underreflux for 24 hours. The ethanol is concentrated by evaporation on arotary evaporator and then the aqueous phase is extracted with 500 ml ofdichloromethane. The aqueous phase is separated and again extracted withdichloromethane (2×). The combined organic phases are washed withsaturated aqueous NaCl solution (1×), dried over MgSO₄ and concentratedby evaporation on a rotary evaporator. From the residue, the titlecompound A1 is obtained as a white solid by flash chromatography (SiO₂60F / dichloromethane / methanol / NH₃, 40:10:1) (11.86g, 75% oftheory).

EXAMPLE A2 Preparation of 1-amino-3-hydroxy-norbornane hydrochloride

[0121] 1 g of A1 is dissolved in 10 ml of ethanol and mixed at roomtemperature with 10 ml of 15% HCl in ethanol. After concentrating byevaporation on a rotary evaporator, a white solid is obtained (1.35 9),which is recrystallised from 22 ml of isopropanol. The title compound A2is thus obtained as a white solid (0.86 g, 67% of theory). Meltingpoint >220 ° C.; ¹H-NMR (400 Hz, DMSO_(d6)) δ: 1.13 (1H); 1.32 (3H);2.08 (2H); 2.21 (1H); 2.41 (1H); 3.55 (1H); 4.40 (1H); 7.70 (3H).

EXAMPLE A3 Preparation of 1-t-butyloxycarbonylamino-3-hydroxy-norbornane(A3)

[0122] 1 g of A1 is dissolved in 5 ml of dichloromethane and mixed with1.75 ml of ethyl-diisopropyl-amine whilst cooling with ice.Subsequently, a solution of 1.89 g of di-tert.-butyl dicarbonate in 10ml of dichloromethane is dispensed in. The white suspension is stirredfor 18 hours at room temperature and subsequently concentrated on arotary evaporator. The residue is mixed with 50 ml of ethyl acetate,washed with water (1×) and saturated aqueous NaCl solution (1×), driedover MgSO₄ and concentrated by evaporation on a rotary evaporator. Fromthe residue, the title compound A3 is obtained as a white solid by flashchromatography (SiO₂ 60F / dichloromethane / methanol, 30:1) (1.45g,83%): ¹H-NMR (400 Hz, DMSO_(d6)) δ: 1.0 (2H); 1.27 (2H); 1.40 (9H); 2.05(2H); 2.18 (2H); 3.95 (1H); 4.30 (1H); 5.52 (1H); 7.12 (1H).

EXAMPLE A4 Preparation of 1-methylamino-3-hydroxy-norbornane (A3)

[0123] A solution of 1.4 g of A3 in 15 ml of tetrahydrofuran isdispensed into a suspension of 0.96 g of lithium aluminium hydride in 20ml of tetrahydrofuran whilst cooling with ice. When this addition iscomplete, the reaction mixture is firstly heated to room temperature andthen stirred under reflux for 18 hours. Then, 10 ml of 2N sodiumhydroxide solution are dispensed in whilst cooling with ice. The whitesuspension is filtered and the filtrate concentrated by evaporation on arotary evaporator. The residue is dissolved in 20 ml of diethylether,washed with saturated aqueous NaCl solution (1×), dried over MgSO₄ andconcentrated by evaporation on a rotary evaporator. From the residue,the title compound A3 is obtained as a colourless oil by bulb tubedistillation (90° C., 0.03 mbars) (0.45 g, 50% of theory).

EXAMPLE A4: Preparation of 1-methylamino-3-hydroxy-norbornanehydrochloride (A4)

[0124] 0.4 g of A3 are dissolved in 4 ml of ethanol and mixed at roomtemperature with 4 ml of 15% HCl in ethanol. After concentrating byevaporation on a rotary evaporator, a white solid is obtained (0.44 g),which is recrystallised from 2 ml of isopropanol. The title compound A4is thus obtained as a white solid (0.2 g, 40%). Melting point 154C.¹H-NMR (400Hz, DMSO_(d6)) δ: 1.13 (1H); 1.38 (3H); 2.05 (2H); 2.25 (1H);2.52 (3H); 3.43 (1H); 4.35 (1H); 5.92 (1H); 8.57 (2H).

EXAMPLE A5 Preparation of 1-p-toluenesulfonylamino-3-hydroxy-norbornane(A5)

[0125] 0.7 g of A1 are dissolved in 7 ml of dichloromethane and mixedwith 0.9 ml of pyridine. 1.05 g of p-toluenesulfochloride are addedwhilst cooling with ice, and the reaction mixture is stirred for 2hours. The mixture is diluted with 50 ml of dichloromethane, washed withwater (1×), dried over MgSO₄ and concentrated by evaporation on a rotaryevaporator. From the residue, the title compound A5 is obtained as awhite solid by flash chromatography (SiO₂ 60F / dichloromethane /methanol 20:1) and subsequent recrystallisation from toluene (0.53 g,35% of theory). Melting point: 110-111° C. ¹H-NMR (400 Hz, DMSO_(d6)) δ:0.92 (2H); 1.14 (2H); 1.90 (4H); 2.40 (3H); 3.70 (1H); 4.22 (1H); 5.72(1H); 7.40 (2H); 7.50 (1H); 7.70 (2H).

EXAMPLE A6 Preparation of A1

[0126] a) Preparation of

[0127] 1.64 g of compound (c) are dissolved in 15 ml ofdimethylformamide under argon and mixed with 565 mg of 50% sodiumhydride whilst cooling with ice. Stirring is effected for 30 minutes,and then 1 ml of methyl iodide is added. The suspension is then stirredat room temperature for 18 hours. The reaction mixture is concentratedby evaporation on a rotary evaporator and the residue taken up with 50ml of dichloromethane and 10 ml of saturated ammonium chloride solution.The organic phase is separated, washed with saturated aqueous NaClsolution (1×), dried over MgSO₄ and concentrated by evaporation on arotary evaporator. After recrystallisation from diisopropylether,compound (d) is obtained as a white solid (1.3 g, 73% of theory). ¹H-NMR(400 Hz, DMSO_(d6)), δ: 1.10 (1H); 1.20 (1H); 1.41 (2H); 1.92 (1H); 2.10(1H); 2.20 (2H); 2.28 (1H); 2.37 (1H); 2.86 (1H); 3.68 (1H); 4.70 (1H).

[0128] b) Preparation of A3

[0129] Starting with 1.53 g of (d), and proceeding as in example A4, thetitle compound A3 is obtained as a colourless oil after purification bybulb tube distillation (0.5 g, 39% of theory).

[0130] B) Dreparation of metal complexes

EXAMPLE B1

[0131] Under an inert gas (argon), 6.1 g (0.010 mmols) of[RUCl₂(4-cumene)]₂, 2.8 mg (0.022 mmols) of compound A1 and 10 ml ofabsolute isopropanol are added in succession to a Schlenk flask. Themixture is stirred for 5 minutes at room temperature. The resultingsolution is subsequently used further as a catalyst solution.

[0132] C) Hydrogenation

EXAMPLE C1Preparation of 1-phenylethanol

[0133] 120 mg (1.0 mmols) of acetophenone are added to the catalystsolution of example B1, and the solution is stirred for 5 minutes atroom temperature. Subsequently, 2.4 ml of a 0.1 M NaOH solution inisopropanol are added, and the reaction is started, After 5 minutes, thereaction is interrupted, and the conversion and enantio-selectivity aredetermined. The conversion is 83%, and the enantiomers purity of theformed 1-phenylethanol is 88% ee.

[0134] Determination of conversion: Determination of conversion iscarried out by gas chromatography (HP 5890A). Conditions: Capillarycolumn DB 17 (50 m); starting temperature (60° C.), rate (3° C./minute),end temperature 140° C. Determination of ee: Enantiomer separation iscarried out by gas chromatography (Carlo Erba) with the capillary columnLipodex A (50m×0.25mm). Conditions: 90° C. isothermic, H₂ as carrier gas(150 kPa).

What we claim is:
 1. Compounds of formula I in the form of theirracemates, mixtures of diastereoisomers or substantially purediastereoisomers,

wherein W signifies a direct bond or C₁-C₄-alkylene, X is a direct bondor C₁-C₄-alkylene, Y is C₁-C₄-alkylene, —O—, —S—, —NR₃—, —NR₃—CHR₄—,—NR₃—CR₄R₅, —SiR₄R₅—, —CHR₄P— or —CR₄R₅O—, R₁ signifies hydrogen,C₁-C₆-alkyl, C₂-C₆-alkenyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl,C₆-C₁₀-aryl, or C₇-C₁₂-aralkyl, R₂ is hydrogen, C₁-C₆-alkyl,C₃-C₈-cycloalkyl, C₆-C₁₀-aryl, or C₇-C₁₂-aralkyl, C₁-C₈-acyl,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylaminocarbonyl,di(C₁-C₆-alkyl)aminocarbonyl, (R₆)₂P(O)—, or R₆SO₂—, R₃ signifiesC₁-C₆-alkyl, cyclohexyl, phenyl or benzyl, R₄ and R₅, independently ofone another, are C₁-C₆-alkyl, cyclohexyl, phenyl or benzyl, and R₆ isC₁-C₆-alkyl, C₁-C₆-halogenalkyl; or cyclohexyl, phenyl or benzyl eitherunsubstituted or substituted by C₁-C₄-alkyl, C₁-C₄-halogenalkyl, orC₁-C₄-alkoxy; whereby aliphatic, saturated or ethylenically unsaturatedand/or aromatic hydrocarbon rings are optionally condensed onto therings of the bicyclic ring system; and the optionally condensed bicyclicring system is unsubstituted or is substituted by C₁-C₆-alkyl,C₁-C₆-alkoxy, cyclohexyl, C₆-C₁₀-aryl, C₇-Cl₂₋aralkyl,C₁-C₄-alkyl-C₆-C₁₀-aryl, C₁-C₄-alkoxy-C₆-C₁₀-aryl,C₁-C₄-alkyl-C₇-C₁₂-aralkyl, C₁-C₄-alkoxy-C₇-C₁₂-aralky; as well as theacid addition salts thereof.
 2. Compounds according to claim 1, in whichW in formula I signifies C₁-C₃-alkylene.
 3. Compounds according to claim2, in which W in formula I signifies C,- or C₂-alkylene.
 4. Compoundsaccording to claim 1, in which X in formula I signifies a direct bond orC₁-C₃-alkylene.
 5. Compounds according to claim 4, in which X in formulaI signifies C₁- or C₂-alkylene.
 6. Compounds according to claim 1, inwhich Y in formula I signifies C₁- or C₂-alkylene.
 7. Compoundsaccording to claim 1, in which W, X and Y are selected in such a waythat, in the bicyclic ring system of formula I, each forms a 4- to8-membered hydrocarbon ring.
 8. Compounds according to claim 7, in whichW, X and Y form a 5- to 7-membered hydrocarbon ring.
 9. Compoundsaccording to claim 1, in which R₂ is C₁-C₄-alkyl, cyclopentyl,cyclohexyl, phenyl, benzyl, C₁-C₄-alkoxycarbonyl or the radical R₆-SO₂-, wherein R₆ is C₁-C₄-alkyl, C₁-C₄-fluoroalkyl, or phenyl eitherunsubstituted or substituted by one or two methyl or trifluoromethyl.10. Compounds according to claim 1, whereby they correspond to formulaIa,

wherein Y signifies —CH₂— or —CH₂CH₂—, and R₂ is H, C₁-C₄-alkyl, orsignifies the radical of formula RB-SO₂—, and Rr represents C₁-C₄-alkyl,phenyl or phenyl substituted by C₁-C₄-alkyl or by trifluoromethyl. 11.Process for the preparation of compounds of formula I according to claim1, in which (a) a compound of formula II

wherein W, X and Y are defined as indicated in claim 1, is reacted witha phosphoric acid ester azide in the presence of an alcohol R—OH,wherein R signifies C₁-C₆-alkyl, C₅-C₈-cycloalkyl,C₅-C₈-cycloalkyl-C₁-C₄-alkyl, benzyl, or benzyl substituted byC₁-C₄-alkyl, to form a compound of formula III,

b) the compound of formula III is cyclised with bromine, iodine or anelectrophilic brominating or iodising agent to form a compound offormula IV, wherein X′ is Br or I,

c) in the compound of formula IV, the halogen is substituted by hydrogento form a compound of formula V,

d) the compound of formula V is hydrolysed or reduced to the compound offormula VI,

e) or in the compound of formula V, the hydrogen atom of the NH group issubstituted by the group R′₂ to form compounds of formula VII, whereinR′₂ signifies C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₆-C₁₀-aryl, orC₇-C₁₂-aralkyl, and then the compounds of formula VlI are hydrolysed orreduced to compounds of formula VII,

f) or the compounds of formula VI are reacted withC₁-C₆-alkoxycarbonates, C₁-C₆-alkylamino- or C₁-C₆-dialkylamino-carbonylhalides, C₁-C₈-carboxylic acid halides, C₁-C₆-alkoxycarbonyl halides,(R₆)₂P(O)-halides or R₆-SO₂-esters or halides, to form compounds offormula IX, wherein R″₂ signifies C₁-C₆-alkoxycarbonyl, C₁-C₈-acyl,C₁-C₆-alkylamino—, C₁-C₆-dialkylaminocarbonyl or the groups(R₆)₂P(O)—und R₆—SO₂—.

g) and in compounds of formulae VI, VIII and IX, the OH group isetherified to compounds of formula X, R′, signifies C₁-C₆-alkyl,C₂-C₆-alkenyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl, C₆-C₁₀-aryl, orC₇-C₁₂₋aralkyl, and R₂ is defined as indicated for formula I,


12. Compounds of formula V,

wherein W, X and Y are defined as indicated for formula I in claim 1,whereby aliphatic, saturated or ethylenically unsaturated and/oraromatic hydrocarbon rings are optionally condensed onto the rings ofthe bicyclic ring system; and the optionally condensed bicyclic ringsystem is unsubstituted or is substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy,cyclohexyl, C₆-C₁₀-aryl, C₇-C₁₂-aralkyl, C₁-C₄-alkyl-C₆-C₁₀-aryl,C₁-C₄-alkoxy-C₆-C₁₀-aryl, C₁-C₄-alkyl-C₇-C₁₂-aralkyl orC₁-C₄-alkoxy-C₇-C₁₂-aralky.
 13. Metal complexes of metals selected fromthe secondary group VII of the periodic table of elements with compoundsof formula I as ligands.
 14. Metal complexes according to claim 13, inwhich the metals are selected from the group Rh, Ir and Ru.
 15. Metalcomplexes according to claim 13, in which they correspond to formula XI,[Ru(arene)(L)(A)]  (XI), wherein A is hydride or chloride, arene isC₆-C₁₆-arene, and L signifies a ligand of formula I according toclaim
 1. 16. Metal complexes according to claim 13, in which theycorrespond to formula XII, [Me(diene)(L)(A1)]  (XII), wherein Me is Rhor Ir, diene signifies an open-chained or cyclic diene, L represents aligand of formula I according to claim 1, and A₁ signifies halide. 17.Metal complexes according to claim 13, in which they correspond toformula XIII, [Me₁Cp(L)A₂]  (XIII), wherein Me, signifies Rh, Ir or Ru,A₂ is hydride or halide, preferably chloride, L signifies a ligand offormula I according to claim 1, and Cp represents an optionallysubstituted cyclopentadienyl or indenyl.
 18. Process for the asymmetrichydrogenation with hydrogen, or transfer hydrogenation with hydrogendonors, of prochiral compounds with carbon- or carbon/hetero atommultiple bonds, which is characterised in that the compounds are reactedat low to elevated temperatures in the presence of catalytic quantitiesof a metal complex according to claim
 13. 19. Process according to claim18, whereby the prochiral compounds correspond to formula XIV, R₇R₈C═D  (XIV), wherein R₇ and R₈ are selected in such a way that the compoundis prochiral, and, independently of one another, represent anopen-chained or cyclic hydrocarbon radical or hetero-hydrocarbon radicalwith hetero atoms selected from the group O, S and N, containing 1 to30, preferably 1 to 20 carbon atoms; D is O or a radical of formulaC═R₉R₁₀ or NR₁₁; R₉ and R₁₀, independently of one another, have the samesignificance as R₇ and R₈; R₁₁ signifies hydrogen, C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, C₃-C₁₂-cycloalkyl, C₃-C₁₂-cycloalkyl-C₁-C₆-alkyl,C₃-C₁₁-heterocycloalkyl, C₃-C₁₁-heterocycloalkyl-C₁-C₆-alkyl,C₆-Cl₄-aryl, C₅-C₁₃-hetero-aryl, C₇-C₁₆-aralkyl or C₆-C₁₄-heteroaralkyl;R₇ and R₈, together with the carbon atom to which they are bonded, forma hydrocarbon ring or hetero-hydrocarbon ring with 3 to 12 ring members;R₇ and R₉, together with the C═C-group to which they are bonded, eachform a hydrocarbon ring or hetero-hydrocarbon ring with 3 to 12 ringmembers; R₇ and R₁₁, together with the C═N-group to which they arebonded, each form a hydrocarbon ring or hetero-hydrocarbon ring with 3to 12 ring members; the hetero atoms in the heterocyclic rings areselected from the group O, S and N; and R₇, R₈, R₉, R₁₀ and R₁₁ areunsubstituted or substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, cyclohexyl,C₆-C₁₀-aryl, C₇-Cl₂-aralkyl, C₁-C₄-alkyl-C₆-C₁₀-aryl,C₁-C₄-alkoxy-C₆-C₁₀-aryl, C₁-C₄-alkyl-C₇-C₁₂-aralkyl,C₁-C₄-alkoxy-C₇-C₁₂-aralkyl, —OH, —CO—OR₇, —CO—NR₈R₉ or —NR₈R₉, whereinR₇ is H, an alkali metal, C₁-C₆-alkyl, cyclohexyl, phenyl or benzyl, andR₈ and R₉, independently of one another, are hydrogen, C₁-C₆-alkyl,cyclohexyl, phenyl or benzyl, or R₈ and R₉together signifytetramethylene, pentamethylene or 3-oxapentylene.
 20. Use of the metalcomplexes according to claim 13 as homogeneous catalysts for thehydrogenation, preferably transfer hydrogenation with hydrogen donors,of prochiral compounds with carbon/carbon or carbon/hetero atom multiplebonds.